Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104018219/jz1648sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104018219/jz1648Isup2.hkl |
CCDC reference: 251296
The title compound was obtained by allowing a 96% ethanol solution of 3,4,7,8-tetramethyl-1,10-phenanthroline (tmph) to diffuse into an equimolar aqueous solution containing zinc acetate and sodium thiosulfate (5 ml of each solution, all concentrations being 0.025 M) After ca six weeks of slow evaporation, a few (colourless) prismatic crystals suitable for X-ray analysis were obtained.
H atoms attached to C atoms and unambiguously defined by the stereochemistry were placed at calculated positions (C—H = 0.93 Å) and allowed to ride. Terminal methyl groups in dmph (C—H = 0.96 Å) were also allowed to rotate, although their low rotational energy barrier may make the positions less well defined. H atoms of water molecules were located from difference Fourier syntheses and refined with restrained O—H and H···H distances of 0.82 (1) and 1.36 (2) Å, respectively. All Uiso(H) values were fixed at 1.2Ueq of the parent atoms.
Data collection: SMART-NT (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 2000); data reduction: SAINT-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick,1994); software used to prepare material for publication: SHELXL97.
[Zn(C16H16N2)(H2O)4](S2O3) | F(000) = 1008 |
Mr = 485.86 | Dx = 1.648 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 112 reflections |
a = 9.894 (2) Å | θ = 2.3–21.1° |
b = 9.887 (2) Å | µ = 1.51 mm−1 |
c = 20.016 (4) Å | T = 299 K |
β = 90.909 (4)° | Prism, colorless |
V = 1957.9 (7) Å3 | 0.28 × 0.16 × 0.12 mm |
Z = 4 |
Bruker CCD area-detector diffractometer | 4386 independent reflections |
Radiation source: fine-focus sealed tube | 1863 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.072 |
ϕ and ω scans | θmax = 28.1°, θmin = 2.0° |
Absorption correction: multi scan [SADABS (Sheldrick, 1996) in SAINT_NT (Bruker, 2000)] | h = −12→12 |
Tmin = 0.75, Tmax = 0.83 | k = 0→12 |
15814 measured reflections | l = 0→26 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.141 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.81 | w = 1/[σ2(Fo2) + (0.0446P)2] where P = (Fo2 + 2Fc2)/3 |
4386 reflections | (Δ/σ)max = 0.012 |
277 parameters | Δρmax = 0.89 e Å−3 |
48 restraints | Δρmin = −0.52 e Å−3 |
[Zn(C16H16N2)(H2O)4](S2O3) | V = 1957.9 (7) Å3 |
Mr = 485.86 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.894 (2) Å | µ = 1.51 mm−1 |
b = 9.887 (2) Å | T = 299 K |
c = 20.016 (4) Å | 0.28 × 0.16 × 0.12 mm |
β = 90.909 (4)° |
Bruker CCD area-detector diffractometer | 4386 independent reflections |
Absorption correction: multi scan [SADABS (Sheldrick, 1996) in SAINT_NT (Bruker, 2000)] | 1863 reflections with I > 2σ(I) |
Tmin = 0.75, Tmax = 0.83 | Rint = 0.072 |
15814 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 48 restraints |
wR(F2) = 0.141 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.81 | Δρmax = 0.89 e Å−3 |
4386 reflections | Δρmin = −0.52 e Å−3 |
277 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Zn | 0.49703 (9) | 0.81116 (8) | 0.20958 (4) | 0.0220 (2) | |
S1 | 0.5629 (2) | 0.2167 (2) | 0.33521 (11) | 0.0417 (6) | |
S2 | 0.48935 (19) | 0.32534 (18) | 0.25931 (9) | 0.0256 (5) | |
O1 | 0.4121 (5) | 0.4370 (5) | 0.2893 (3) | 0.0429 (16) | |
O2 | 0.3977 (5) | 0.2418 (5) | 0.2170 (2) | 0.0337 (14) | |
O3 | 0.5999 (5) | 0.3775 (5) | 0.2174 (3) | 0.0405 (15) | |
N1 | 0.4057 (6) | 0.7098 (6) | 0.1260 (3) | 0.0283 (15) | |
N2 | 0.5969 (6) | 0.8993 (6) | 0.1271 (3) | 0.0254 (15) | |
C1 | 0.3114 (8) | 0.6182 (7) | 0.1243 (4) | 0.035 (2) | |
H1A | 0.2727 | 0.5968 | 0.1650 | 0.042* | |
C2 | 0.2601 (8) | 0.5460 (8) | 0.0670 (4) | 0.037 (2) | |
C3 | 0.3195 (8) | 0.5744 (8) | 0.0074 (4) | 0.036 (2) | |
C4 | 0.4227 (8) | 0.6788 (7) | 0.0064 (4) | 0.036 (2) | |
C5 | 0.4910 (8) | 0.7194 (8) | −0.0519 (3) | 0.036 (2) | |
H5A | 0.4686 | 0.6787 | −0.0924 | 0.044* | |
C6 | 0.5884 (9) | 0.8161 (9) | −0.0501 (4) | 0.050 (3) | |
H6A | 0.6285 | 0.8422 | −0.0898 | 0.061* | |
C7 | 0.6302 (8) | 0.8778 (8) | 0.0099 (4) | 0.032 (2) | |
C8 | 0.7297 (8) | 0.9847 (9) | 0.0122 (4) | 0.041 (2) | |
C9 | 0.7599 (8) | 1.0404 (8) | 0.0723 (4) | 0.036 (2) | |
C10 | 0.6893 (7) | 0.9932 (7) | 0.1290 (4) | 0.032 (2) | |
H10A | 0.7104 | 1.0318 | 0.1702 | 0.039* | |
C11 | 0.5641 (8) | 0.8433 (7) | 0.0659 (4) | 0.0299 (19) | |
C12 | 0.4621 (8) | 0.7402 (7) | 0.0667 (4) | 0.0271 (19) | |
C13 | 0.1488 (8) | 0.4448 (8) | 0.0746 (4) | 0.054 (3) | |
H13A | 0.1850 | 0.3551 | 0.0709 | 0.081* | |
H13B | 0.0815 | 0.4589 | 0.0402 | 0.081* | |
H13C | 0.1085 | 0.4556 | 0.1176 | 0.081* | |
C14 | 0.2760 (9) | 0.5017 (9) | −0.0534 (4) | 0.056 (3) | |
H14A | 0.2209 | 0.4258 | −0.0414 | 0.085* | |
H14B | 0.3540 | 0.4704 | −0.0767 | 0.085* | |
H14C | 0.2246 | 0.5616 | −0.0818 | 0.085* | |
C15 | 0.7968 (7) | 1.0231 (9) | −0.0484 (4) | 0.062 (3) | |
H15A | 0.8653 | 1.0891 | −0.0382 | 0.092* | |
H15B | 0.7321 | 1.0610 | −0.0794 | 0.092* | |
H15C | 0.8378 | 0.9448 | −0.0680 | 0.092* | |
C16 | 0.8606 (8) | 1.1511 (8) | 0.0780 (4) | 0.062 (3) | |
H16A | 0.8248 | 1.2312 | 0.0571 | 0.093* | |
H16B | 0.9422 | 1.1248 | 0.0561 | 0.093* | |
H16C | 0.8799 | 1.1691 | 0.1243 | 0.093* | |
O1W | 0.6413 (5) | 0.6560 (5) | 0.2223 (3) | 0.0413 (15) | |
H1WA | 0.603 (3) | 0.5845 (15) | 0.213 (3) | 0.050* | |
H1WB | 0.705 (3) | 0.673 (4) | 0.198 (3) | 0.050* | |
O2W | 0.3602 (5) | 0.9699 (5) | 0.2191 (3) | 0.0437 (16) | |
H2WA | 0.293 (3) | 0.960 (4) | 0.196 (3) | 0.052* | |
H2WB | 0.398 (2) | 1.0427 (14) | 0.217 (3) | 0.052* | |
O3W | 0.6169 (5) | 0.9082 (5) | 0.2824 (3) | 0.0339 (14) | |
H3WA | 0.6962 (12) | 0.899 (5) | 0.272 (2) | 0.041* | |
H3WB | 0.596 (4) | 0.9885 (18) | 0.284 (2) | 0.041* | |
O4W | 0.3851 (5) | 0.7146 (5) | 0.2838 (3) | 0.0371 (14) | |
H4WB | 0.309 (2) | 0.747 (4) | 0.286 (2) | 0.045* | |
H4WA | 0.388 (5) | 0.6330 (11) | 0.279 (2) | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn | 0.0298 (5) | 0.0162 (4) | 0.0199 (4) | −0.0002 (5) | −0.0012 (4) | −0.0003 (4) |
S1 | 0.0409 (15) | 0.0349 (13) | 0.0494 (14) | 0.0043 (11) | −0.0002 (12) | 0.0052 (11) |
S2 | 0.0235 (11) | 0.0165 (10) | 0.0371 (11) | −0.0019 (9) | 0.0026 (9) | 0.0015 (9) |
O1 | 0.025 (3) | 0.018 (3) | 0.086 (5) | −0.001 (3) | 0.009 (3) | −0.022 (3) |
O2 | 0.029 (3) | 0.029 (3) | 0.043 (3) | −0.008 (3) | −0.002 (3) | −0.002 (3) |
O3 | 0.026 (3) | 0.034 (3) | 0.063 (4) | −0.005 (3) | 0.015 (3) | −0.019 (3) |
N1 | 0.033 (4) | 0.020 (4) | 0.032 (4) | 0.000 (3) | −0.001 (3) | 0.003 (3) |
N2 | 0.037 (4) | 0.027 (4) | 0.012 (3) | 0.005 (3) | −0.002 (3) | 0.001 (3) |
C1 | 0.046 (6) | 0.032 (5) | 0.027 (5) | 0.011 (4) | −0.007 (4) | −0.011 (4) |
C2 | 0.033 (5) | 0.041 (5) | 0.038 (5) | 0.002 (4) | −0.004 (4) | 0.010 (4) |
C3 | 0.034 (5) | 0.039 (5) | 0.033 (5) | 0.010 (4) | −0.015 (4) | −0.012 (4) |
C4 | 0.044 (6) | 0.032 (5) | 0.032 (5) | 0.014 (5) | −0.010 (4) | −0.006 (4) |
C5 | 0.053 (6) | 0.045 (5) | 0.012 (4) | 0.006 (5) | −0.006 (4) | −0.004 (4) |
C6 | 0.048 (6) | 0.073 (7) | 0.031 (5) | 0.017 (6) | 0.011 (5) | 0.017 (5) |
C7 | 0.035 (5) | 0.047 (5) | 0.014 (4) | 0.014 (4) | 0.002 (4) | 0.005 (4) |
C8 | 0.027 (6) | 0.060 (6) | 0.038 (6) | 0.014 (5) | 0.009 (5) | 0.008 (5) |
C9 | 0.027 (5) | 0.033 (5) | 0.047 (6) | 0.001 (4) | 0.004 (4) | 0.008 (4) |
C10 | 0.037 (5) | 0.025 (4) | 0.035 (5) | −0.003 (4) | −0.005 (4) | 0.008 (4) |
C11 | 0.025 (5) | 0.033 (5) | 0.032 (5) | 0.007 (4) | 0.006 (4) | 0.000 (4) |
C12 | 0.031 (5) | 0.024 (4) | 0.026 (5) | 0.003 (4) | 0.002 (4) | 0.001 (3) |
C13 | 0.055 (7) | 0.038 (5) | 0.067 (7) | −0.003 (5) | −0.016 (5) | −0.005 (5) |
C14 | 0.049 (7) | 0.068 (7) | 0.052 (6) | −0.006 (6) | −0.004 (5) | −0.014 (5) |
C15 | 0.044 (7) | 0.061 (7) | 0.080 (8) | 0.010 (5) | 0.002 (6) | 0.025 (6) |
C16 | 0.053 (7) | 0.054 (6) | 0.079 (7) | −0.012 (5) | −0.001 (6) | 0.023 (5) |
O1W | 0.031 (4) | 0.018 (3) | 0.075 (4) | 0.000 (3) | 0.007 (3) | −0.001 (3) |
O2W | 0.034 (4) | 0.025 (3) | 0.072 (5) | −0.002 (3) | 0.003 (3) | −0.006 (3) |
O3W | 0.031 (3) | 0.023 (3) | 0.048 (4) | −0.001 (3) | 0.004 (3) | −0.008 (3) |
O4W | 0.032 (3) | 0.016 (3) | 0.063 (4) | 0.001 (3) | 0.013 (3) | 0.005 (3) |
Zn—O2W | 2.084 (5) | C7—C8 | 1.444 (9) |
Zn—O4W | 2.097 (5) | C8—C9 | 1.353 (9) |
Zn—O3W | 2.097 (5) | C8—C15 | 1.443 (9) |
Zn—O1W | 2.108 (5) | C9—C10 | 1.421 (8) |
Zn—N2 | 2.124 (6) | C9—C16 | 1.483 (8) |
Zn—N1 | 2.138 (6) | C10—H10A | 0.93 |
S1—S2 | 1.989 (3) | C11—C12 | 1.435 (10) |
S2—O1 | 1.475 (5) | C13—H13A | 0.96 |
S2—O3 | 1.482 (5) | C13—H13B | 0.96 |
S2—O2 | 1.482 (5) | C13—H13C | 0.96 |
N1—C1 | 1.300 (7) | C14—H14A | 0.96 |
N1—C12 | 1.353 (9) | C14—H14B | 0.96 |
N2—C10 | 1.303 (7) | C14—H14C | 0.96 |
N2—C11 | 1.378 (9) | C15—H15A | 0.96 |
C1—C2 | 1.436 (8) | C15—H15B | 0.96 |
C1—H1A | 0.93 | C15—H15C | 0.96 |
C2—C3 | 1.368 (9) | C16—H16A | 0.96 |
C2—C13 | 1.498 (8) | C16—H16B | 0.96 |
C3—C4 | 1.452 (9) | C16—H16C | 0.96 |
C3—C14 | 1.471 (8) | O1W—H1WA | 0.82 (2) |
C4—C12 | 1.402 (9) | O1W—H1WB | 0.82 (4) |
C4—C5 | 1.416 (8) | O2W—H2WA | 0.81 (4) |
C5—C6 | 1.358 (10) | O2W—H2WB | 0.813 (16) |
C5—H5A | 0.93 | O3W—H3WA | 0.820 (16) |
C6—C7 | 1.403 (8) | O3W—H3WB | 0.82 (2) |
C6—H6A | 0.93 | O4W—H4WA | 0.813 (13) |
C7—C11 | 1.351 (9) | O4W—H4WB | 0.82 (3) |
O2W—Zn—O4W | 85.8 (2) | C15—C8—C7 | 119.2 (8) |
O2W—Zn—O3W | 87.3 (2) | C8—C9—C10 | 118.2 (7) |
O4W—Zn—O3W | 90.9 (2) | C8—C9—C16 | 120.5 (7) |
O2W—Zn—O1W | 167.6 (2) | C10—C9—C16 | 121.3 (7) |
O4W—Zn—O1W | 87.0 (2) | N2—C10—C9 | 124.4 (7) |
O3W—Zn—O1W | 82.8 (2) | N2—C10—H10A | 117.8 |
O2W—Zn—N2 | 94.2 (2) | C9—C10—H10A | 117.8 |
O4W—Zn—N2 | 174.1 (2) | C7—C11—N2 | 121.8 (7) |
O3W—Zn—N2 | 95.0 (2) | C7—C11—C12 | 122.6 (7) |
O1W—Zn—N2 | 94.1 (2) | N2—C11—C12 | 115.5 (7) |
O2W—Zn—N1 | 99.1 (2) | N1—C12—C4 | 123.1 (7) |
O4W—Zn—N1 | 96.8 (2) | N1—C12—C11 | 117.9 (7) |
O3W—Zn—N1 | 170.3 (2) | C4—C12—C11 | 119.0 (7) |
O1W—Zn—N1 | 91.8 (2) | C2—C13—H13A | 109.4 |
N2—Zn—N1 | 77.3 (2) | C2—C13—H13B | 109.6 |
O1—S2—O3 | 111.2 (3) | H13A—C13—H13B | 109.5 |
O1—S2—O2 | 109.4 (3) | C2—C13—H13C | 109.4 |
O3—S2—O2 | 108.7 (3) | H13A—C13—H13C | 109.5 |
O1—S2—S1 | 106.2 (3) | H13B—C13—H13C | 109.5 |
O3—S2—S1 | 110.8 (2) | C3—C14—H14A | 109.6 |
O2—S2—S1 | 110.4 (2) | C3—C14—H14B | 109.4 |
C1—N1—C12 | 116.0 (7) | H14A—C14—H14B | 109.5 |
C1—N1—Zn | 129.9 (5) | C3—C14—H14C | 109.4 |
C12—N1—Zn | 114.0 (5) | H14A—C14—H14C | 109.5 |
C10—N2—C11 | 117.8 (6) | H14B—C14—H14C | 109.5 |
C10—N2—Zn | 127.2 (5) | C8—C15—H15A | 109.5 |
C11—N2—Zn | 114.8 (5) | C8—C15—H15B | 109.4 |
N1—C1—C2 | 127.7 (7) | H15A—C15—H15B | 109.5 |
N1—C1—H1A | 116.1 | C8—C15—H15C | 109.5 |
C2—C1—H1A | 116.2 | H15A—C15—H15C | 109.5 |
C3—C2—C1 | 116.3 (7) | H15B—C15—H15C | 109.5 |
C3—C2—C13 | 123.5 (7) | C9—C16—H16A | 109.4 |
C1—C2—C13 | 120.2 (6) | C9—C16—H16B | 109.6 |
C2—C3—C4 | 118.0 (7) | H16A—C16—H16B | 109.5 |
C2—C3—C14 | 119.8 (8) | C9—C16—H16C | 109.5 |
C4—C3—C14 | 122.2 (7) | H16A—C16—H16C | 109.5 |
C12—C4—C5 | 117.2 (7) | H16B—C16—H16C | 109.5 |
C12—C4—C3 | 118.9 (7) | Zn—O1W—H1WA | 107.2 (19) |
C5—C4—C3 | 123.9 (7) | Zn—O1W—H1WB | 108.2 (19) |
C6—C5—C4 | 121.8 (7) | H1WA—O1W—H1WB | 114 (3) |
C6—C5—H5A | 119.1 | Zn—O2W—H2WA | 112 (2) |
C4—C5—H5A | 119.1 | Zn—O2W—H2WB | 111 (2) |
C5—C6—C7 | 121.9 (7) | H2WA—O2W—H2WB | 117 (3) |
C5—C6—H6A | 119.1 | Zn—O3W—H3WA | 107.5 (19) |
C7—C6—H6A | 119.0 | Zn—O3W—H3WB | 109.2 (18) |
C11—C7—C6 | 117.4 (8) | H3WA—O3W—H3WB | 112 (3) |
C11—C7—C8 | 119.8 (7) | Zn—O4W—H4WB | 110.6 (19) |
C6—C7—C8 | 122.5 (8) | Zn—O4W—H4WA | 110.3 (19) |
C9—C8—C15 | 122.9 (8) | H4WB—O4W—H4WA | 115 (3) |
C9—C8—C7 | 117.8 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O3 | 0.82 (2) | 2.05 (2) | 2.785 (7) | 150 (3) |
O1W—H1WB···S1i | 0.82 (4) | 2.44 (2) | 3.219 (6) | 160 (5) |
O2W—H2WA···O1ii | 0.81 (4) | 2.07 (4) | 2.716 (8) | 136 (6) |
O2W—H2WB···O2iii | 0.81 (2) | 1.97 (1) | 2.714 (7) | 153 (3) |
O3W—H3WA···O3i | 0.82 (2) | 2.04 (2) | 2.818 (7) | 159 (4) |
O3W—H3WB···S1iii | 0.82 (2) | 2.50 (1) | 3.275 (5) | 158 (3) |
O4W—H4WA···O1 | 0.81 (1) | 1.96 (2) | 2.760 (6) | 166 (6) |
O4W—H4WB···O2ii | 0.82 (3) | 2.05 (3) | 2.811 (7) | 156 (5) |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C16H16N2)(H2O)4](S2O3) |
Mr | 485.86 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 299 |
a, b, c (Å) | 9.894 (2), 9.887 (2), 20.016 (4) |
β (°) | 90.909 (4) |
V (Å3) | 1957.9 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.51 |
Crystal size (mm) | 0.28 × 0.16 × 0.12 |
Data collection | |
Diffractometer | Bruker CCD area-detector diffractometer |
Absorption correction | Multi scan [SADABS (Sheldrick, 1996) in SAINT_NT (Bruker, 2000)] |
Tmin, Tmax | 0.75, 0.83 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15814, 4386, 1863 |
Rint | 0.072 |
(sin θ/λ)max (Å−1) | 0.662 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.141, 0.81 |
No. of reflections | 4386 |
No. of parameters | 277 |
No. of restraints | 48 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.89, −0.52 |
Computer programs: SMART-NT (Bruker, 2001), SAINT-NT (Bruker, 2000), SAINT-NT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL/PC (Sheldrick,1994), SHELXL97.
Zn—O2W | 2.084 (5) | Zn—N1 | 2.138 (6) |
Zn—O4W | 2.097 (5) | S1—S2 | 1.989 (3) |
Zn—O3W | 2.097 (5) | S2—O1 | 1.475 (5) |
Zn—O1W | 2.108 (5) | S2—O3 | 1.482 (5) |
Zn—N2 | 2.124 (6) | S2—O2 | 1.482 (5) |
O1—S2—O3 | 111.2 (3) | O1—S2—S1 | 106.2 (3) |
O1—S2—O2 | 109.4 (3) | O3—S2—S1 | 110.8 (2) |
O3—S2—O2 | 108.7 (3) | O2—S2—S1 | 110.4 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O3 | 0.82 (2) | 2.048 (17) | 2.785 (7) | 150 (3) |
O1W—H1WB···S1i | 0.82 (4) | 2.439 (19) | 3.219 (6) | 160 (5) |
O2W—H2WA···O1ii | 0.81 (4) | 2.07 (4) | 2.716 (8) | 136 (6) |
O2W—H2WB···O2iii | 0.813 (16) | 1.969 (14) | 2.714 (7) | 153 (3) |
O3W—H3WA···O3i | 0.820 (16) | 2.036 (16) | 2.818 (7) | 159 (4) |
O3W—H3WB···S1iii | 0.82 (2) | 2.499 (12) | 3.275 (5) | 158 (3) |
O4W—H4WA···O1 | 0.813 (13) | 1.964 (16) | 2.760 (6) | 166 (6) |
O4W—H4WB···O2ii | 0.82 (3) | 2.05 (3) | 2.811 (7) | 156 (5) |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) x, y+1, z. |
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The thiosulfate anion (S2O3)2− is a highly versatile ligand, and metal complexes in which it does not bind to the cation are not common. A search of the April 2004 version of the Cambridge Structural Database (Allen, 2002) shows that fewer than 20% of the reported structures containing thiosulfate contain the group acting as a counter-ion; in the remaining cases it coordinates in a variety of different binding modes [for a brief review on the subject see Freire et al. (2000), and references therein]. This behavior contrasts with those of some closely related oxyanions, e.g. sulfate, where the ratio rises to ca 50%.
When the anion does not coordinate, it tends to be involved in non-bonding interactions that are unusual either by virtue of their nature, as in Ni(bpy)3·S2O3·7(H2O), (bpy is 2,2'-bipyridine; Freire et al., 2000) where two neighboring thiosulfates approach linearly head to head via a strikingly short S···S contact of 3.25 Å, or because of their quantity, as in the organic clathrate C36H60N86+·S2O32−·4ClO4−.11H2O (Maubert et al., 2001), in which the anion in involved in 12 strong hydrogen-bonding interactions.
We present here the structure of the monomeric zinc(II) complex with thiosulfate and 3,4,7,8-tetramethyl-1,10-phenanthroline (tmph), [Zn(tmph)(H2O)4](S2O3), (I), one of the infrequent cases in which the anion does not bind to the cationic unit directly but is multiply connected through a dense network of hydrogen bonds.
The structure is shown in Fig. 1. The N2O4 environment about the Zn atom is achieved through two N-donors of the tmph ligand [which imposes the only distortion to the coordination polyhedron through its small bite angle, 77.6 (2)°] and four water donor molecules. The result is a slightly distorted octahedral coordination with a fairly narrow range of metal–N,O bond lengths [2.101 (5)–2.146 (5) Å].
Analogous monomeric complexes with unsubstituted 1,10-phenanthroline instead of tmph molecules have been reported previously in the form of [Zn(phen)(H2O)4]−2, the counter-ion(s) being either SO42− (Zang et al., 1999) or 2NO3− (Zhang and Janiak, 2001). No major differences are observed between these complexes and the present structure; a least-squares fit yielded mean deviations of 0.15 (1) and 0.12 (1) Å, respectively, for all the 19 atoms they have in common.
The tmph group is essentially planar [the mean deviation from the plane is 0.02 (1) Å] and binds to the cation with a small, though detectable, tilt [the angle between the N1/Zn/N2 and tmph planes is 6.4 (1)°].
As expected, the thiosulfate anion has an undistorted structure, with three S—O bond lengths that are undistinguishable within experimental error. A slight departure from the ideal arrangement is observed for the S—S—O angles, presumably arising from asymmetries in non-bonding contacts.
The packing of the structure is governed by the hydrogen-bonding interactions involving, as donors, all eight water H atoms and, as acceptors, the outer atoms of the thiosulfate anion (one S and three O), all of them fulfilling the role of double acceptors. This `one-to-one' correspondence results in an approximately square geometry (in projection) of the hydrogen-bonding network around the thiosulfate anion (Fig. 2), and in turn in a two-dimensional structure perpendicular to the c axis, in which each complex interacts with four counter-ions and vice versa (Table 2). The two-dimensional frameworks thus defined are concentrated in narrow regions at z ~0.25 and z ~0.75, with the bulky dmph groups protruding outwards from opposite `faces' of the two-dimensional arrays, those on one side being at 90° to those on the other (Fig. 3). Neighboring planes are related by inversion centers promoting the interleaving of parallel aromatic groups at graphitic distance from each other. These π–π interacting groups are separated by 3.48 (1) Å, with overlapping rings slipped by 18.3 (1)° [where the slippage angle is that subtended by the ring normal and the center-to-center line (Janiak, 2000)].